BT8302 Atb Question Bank PDF

JEPPIAAR ENGINEERING COLLEGE
B.TECH – BIOTECHNOLOGY (R- 2017)
BT 8302 APPLIED THERMODYNAMICS FOR

BIOTECHNOLOGISTS
II YEAR & III SEM
BATCH: 2017-2021
QUESTION BANK
PREPARED BY
A.MUTHULAKSHMI
1
VISION OF THE INSTITUTION
 To build Jeppiaar Engineering College as an institution of academic excellence in technological and
management education to become a world class University
MISSION OF THE INSTITUTION
 To excel in teaching and learning, research and innovation by promoting the principles of scientific
analysis and creative thinking.
 To participate in the production, development and dissemination of knowledge and interact with national
and international communities.
 To equip students with values, ethics and life skills needed to enrich their lives and enable them to
meaningfully contribute to the progress of society.
 To prepare students for higher studies and lifelong learning, enrich them with the practical and
entrepreneurial skills necessary to excel as future professionals and contribute to Nation’s economy
PROGRAM OUTCOMES (PO)

Engineering knowledge: Apply the knowledge of mathematics, science, engineering
PO 1
fundamentals, and an engineering specialization to the solution of complex engineering problems.
Problem analysis: Identify, formulate, review research literature, and analyze complex
PO 2 engineering problems reaching substantiated conclusions using first principles of mathematics,
natural sciences, and engineering sciences.
Design/development of solutions: Design solutions for complex engineering problems and
design system components or processes that meet the specified needs with appropriate
PO 3
consideration for the public health and safety, and the cultural, societal, and environmental
considerations
Conduct investigations of complex problems: Use research-based knowledge and research
PO 4 methods including design of experiments, analysis and interpretation of data, and synthesis of
the information to provide valid conclusions.
Modern tool usage: Create, select, and apply appropriate techniques, resources, and modern
PO 5 engineering and IT tools including prediction and modeling to complex engineering activities with an
understanding of the limitations.
The engineer and society: Apply reasoning informed by the contextual knowledge to assess
PO 6 societal, health, safety, legal and cultural issues and the consequent responsibilities relevant to the
professional engineering practice.
Environment and sustainability: Understand the impact of the professional engineering solutions
PO 7 in societal and environmental contexts, and demonstrate the knowledge of, and need for
sustainable development.
Ethics: Apply ethical principles and commit to professional ethics and responsibilities and norms of
PO 8
the engineering practice.
Individual and team work: Function effectively as an individual, and as a member or leader in
PO 9
diverse teams, and in multidisciplinary settings.
Communication: Communicate effectively on complex engineering activities with the
engineering community and with society at large, such as, being able to comprehend and write
PO 10
effective reports and design documentation, make effective presentations, and give and receive
clear instructions.
Project management and finance: Demonstrate knowledge and understanding of the
PO 11 engineering and management principles and apply these to one’s own work, as a member and
leader in a team, to manage projects and in multidisciplinary environments.
Life-long learning: Recognize the need for, and have the preparation and ability to engage in
PO 12
independent and life-long learning in the broadest context of technological change.
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VISION OF THE DEPARTMENT
To pursue excellence in producing bioengineers coupled with research attributes.
MISSION OF THE DEPARTMENT

M1 To impart quality education and transform technical knowledge into career opportunities.
M2 To establish a bridge between the program and society by fostering technical education.
M3 To generate societal conscious technocrats towards community development

To facilitate higher studies and research in order to have an effective career /
M4
entrepreneurship.
PROGRAM EDUCATIONAL OBJECTIVES (PEOS)

PEO - 1 To impart knowledge and produce competent graduates in the field of biotechnology
To inculcate professional attributes and ability to integrate engineering issues to broader social
PEO - 2
contexts.
PEO - 3 To connect the program and community by fostering technical education.
PEO - 4 To provide a wide technical exposure to work in an interdisciplinary environment
PEO - 5 To prepare the students to have a professional career and motivation towards higher education.
PROGRAM SPECIFIC OUTCOMES (PSOS)

Professional Skills: This programme will provide students with a solid foundation in the field
PSO 1 of Biological Sciences and Chemical engineering enabling them to work on engineering
platforms and applications in Biotechnology as per the requirement of Industries, and
facilitating the students to pursue higher studies
Problem-solving skills: This programme will assist the students to acquire fundamental and
PSO 2 problem solving knowledge on subjects relevant to Biotechnology thereby encouraging them to
understand emerging and advanced concepts in modern biology
Successful Career and Entrepreneurship: Graduates of the program will have a strong
PSO 3 successful career and entrepreneurial ability with the blend of inputs from basic science,
engineering and technology, thereby enabling them to translate the technology and tools in
various industries and/or institutes
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BT8302 APPLIED THERMODYNAMICS FOR BIOTECHNOLOGISTS
UNIT I -THERMODYNAMIC LAW AND PROPERTIES OF FLUIDS(9)
First Law of thermodynamics, a generalized balance equation and conserved quantities, Volumetric
properties of fluids exhibiting non ideal behavior; residual properties; estimation of thermodynamic
properties using equations of state; calculations involving actual property exchanges; Maxwell’s
relations and applications.
UNIT II - SOLUTION THERMODYNAMICS (9)
Partial molar properties; concepts of chemical potential and fugacity; ideal and non-ideal solutions;
concepts and applications of excess properties of mixtures; activity coefficient; composition models;
Gibbs Duhem equation.
UNIT III - PHASE EQUILIBRIA(9)
Criteria for phase equilibria; VLE calculations for binary and multi component systems; liquid- liquid
equilibria and solid-solid equilibria.
UNIT IV- CHEMICAL REACTION EQUILIBRIA (9)
Equilibrium criteria for homogeneous chemical reactions; evaluation of equilibrium constant; effect of
temperature and pressure on equilibrium constant; calculation of equilibrium conversion and yields for
single and multiple reactions.
UNIT V -THERMODYNAMIC DESCRIPTION OF MICROBIALGROWTH AND PRODUCT
FORMATION (9)
Thermodynamics of microbial growth stoichiometry thermodynamics of maintenance, Calculation of
the Operational Stoichiometry of a growth process at Different growth rates, Including Heat using the
Herbert –Pirt Relation for Electron Donor, thermodynamics and stoichiometry of Product Formation.
TEXT BOOKS:
1. Smith J.M., Van Ness H.C., and Abbot M.M. “Introduction to Chemical Engineering
Thermodynamics”, 6th Edition. Tata McGraw-Hill, 2003.
2. Narayanan K.V. “A Text Book of Chemical Engineering Thermodynamics”, PHI,2003.
3. Christiana D. Smolke, “ The Metabolic Pathway Engineering Handbook Fundamentals”,CRC
Press Taylor & Francis Group, 2010.
REFERENCE:
1. Sandler S.I. “Chemical and Engineering Thermodynamics”, John Wiley,1989.
BT 8302 APPLIED THERMODYNAMICS FOR BIOTECHNOLOGISTS

CO NO. COURSE OUTCOMES
C211.1 Able to describe the knowledge on thermodynamic law and properties of fluids
C211.2 Able to understand the concept of solution thermodynamics
C211.3 Able to understand the phase equilibria in liquid liquid and solid –solid equilibria
C211.4 understand the concept of chemical reaction equilibria
Ability to apply the thermodynamic description of microbial  growth and product
C211.5
formation
4
S.
Title Reference Book Page No.
No.
UNIT I -THERMODYNAMIC LAW AND PROPERTIES OF FLUIDS (9)
Narayanan K.V“A Text
Book of Chemical
1. First Law of thermodynamics 23-30
Engineering
Thermodynamics” (CET)
2. A generalized balance equation and conserved quantities Narayanan K.V (CET) 31-32
3. Volumetric properties of fluids exhibiting non ideal behavior; Narayanan K.V (CET) 188-191
4. Residual properties Narayanan K.V (CET) 237-240
5. Estimation of thermodynamic properties using equations of state Narayanan K.V (CET) 191-216
6. Calculations involving actual property exchanges Narayanan K.V (CET) 288-291
7. Maxwell’s relations and applications. Narayanan K.V (CET) 192-195
UNIT II - SOLUTION THERMODYNAMICS (9)
1. Partial molar properties Narayanan K.V (CET) 257-262
2. Concepts of chemical potential and fugacity Narayanan K.V (CET) 265-273
3. Ideal and non-ideal solutions Narayanan K.V (CET) 273-275
4. Concepts and applications of excess properties of mixtures. Narayanan K.V (CET) 298-300
5. Activity coefficient Narayanan K.V (CET) 278-282
6. Composition models Narayanan K.V (CET) 288-294
7. Gibbs Duhem equation Narayanan K.V (CET) 283-285
UNIT III - PHASE EQUILIBRIA (9)
1. Criteria for phase equilibria Narayanan K.V (CET) 310-312
2. VLE calculations for binary and multi component systems Narayanan K.V (CET) 315-380
3. Liquid- liquid equilibria and Narayanan K.V (CET) 381-383
4. Solid-solid equilibria. Narayanan K.V (CET) REF.PAPER
UNIT IV- CHEMICAL REACTION EQUILIBRIA (9)
1. Equilibrium criteria for homogeneous chemical reactions Narayanan K.V (CET) 398-404
2. Evaluation of equilibrium constant Narayanan K.V (CET) 404-408
3. Effect of temperature and pressure on equilibrium constant Narayanan K.V (CET) 409-421
Calculation of equilibrium conversion and yields for single and
4. Narayanan K.V (CET) 422-439
multiple reactions.
UNIT V -THERMODYNAMIC DESCRIPTION OF MICROBIAL  GROWTH AND PRODUCT FORMATION (9)
Christiana D. Smolke, “
Thermodynamics of microbial growth stoichiometry The Metabolic Pathway
1. 11-2, 11-13
thermodynamics of maintenance Engineering Handbook
Fundamentals”
Calculation of the Operational Stoichiometry of a growth process at
2. Different growth rates, Including Heat using the Herbert –Pirt Christiana D. Smolke 11-14
Relation for Electron Donor
3. Thermodynamics and stoichiometry of Product Formation. Christiana D. Smolke 11-17
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UNIT I -THERMODYNAMIC LAW AND PROPERTIES OF FLUIDS
PART A
1. What are the limitations of first law of thermodynamics? (Apr/May 2017)
(i) The first law of thermodynamics is a law of conservation of energy. It does not specify the direction
of the process. All spontaneous processes processed in one direction only.
(ii) The first law of thermodynamics does not specify the feasibility of a process reversing itself.
(iii) This Law is silent about its % of conversion of energy from one form to another form. Work can be
converted into equivalent amount of heat but heat cannot be converted into equivalent amount of work.
(iv) Mathematically first law of thermodynamics is dU = dQ-dW. Thus first law gives the term of
internal energy ’U’.
2. What is ‘equation of state’? (Apr/May 2017)

An equation of state is a functional relationship between state variables P, T and V.
Ideal gas equation of state is PV = RT.
This equation was established from the postulates of the kinetic theory of gases by Maxwell with the
following assumptions:
(1) There is little or no attraction between the molecules of the gas
(2) Volume occupied by the molecules is negligibly small compared to the volume of gas
Applicability: Ideal gas equation of state is applicable to gas with very small pressure or very high
temperature.
3. Discuss on volume expansivity. (May/June 2016)

It is a parameter that is used to measure the volume expansivity of pure substances and is defined at
constant pressure, P. In the field of materials science, the property of linear coefficient of thermal
expansion is an important consideration in materials selection and design of products. This property is
used to account for the change in volume when the temperature of the material is changed.
4. Define the principle of corresponding states. (May/June 2016)

All gases when compared at the same reduced temperature and reduced pressure, have approximately the
same compressibility factor and all deviate from the ideal behavior to the same extent. Z  f (Tr , Pr )
5. Distinguish between internal energy, kinetic energy and potential energy of a system.(Apr/May 2015)
S.No. Internal Energy Kinetic Energy Potential Energy
1 The system possesses by The energy possessed by the The energy possessed by the system
virtue of the molecular body by virtue of its motion due to its position above some
configuration and motion is called its kinetic energy. arbitrary reference plane is referred to
of molecules. (KE) as its potential energy. (PE)
Unit of energy is joule.
2 1J = 1 Nm = 1kg m2/s2 KE = ½ mv2 PE = mgz
3 Internal energy is a Kinetic Energy is not a Potential Energy is not a

thermodynamic property thermodynamic property of thermodynamic property of the
of the system. the system. It doesn’t change system. It doesn’t change with change
with change in the in the temperature or pressure of the
temperature or pressure of the body.
body.
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6. What are the Maxwell’s equations and what is their importance in establishing relationships between
thermodynamic properties? (Apr/May 2015)
Maxwell’s equations are helpful in replacing unmeasurable quantities appearing in thermodynamic
equations by measurable quantities. Using these relations, the partial derivatives of entropy with respect
to pressure and volume are expressed as derivatives possessing easily identifiable physical meaning.
Each of the four Maxwell’s equations is derived from the exact differential equations of the four energy
properties.
 T   P 
      1
 V  S  S V
 T   V 
    2
 P  S  S  P
 P   S 
    3
 T V  V T
 V   S 
      4
 T  P  P T
7. Distinguish between state and path function. (May/June 2014) (May/June 2007)
State Function Path Function
Depends only on the state at the Dependent on path taken to

moment and independent of path establish property or value.
taken to establish property or value.
Can integrate using final and initial Need multiple integrals and limits
values. of integration in order to integrate.
Multiple steps result in same value. Multiple steps result in different
value.
Based on established state of system Based on how state of system was
(temperature, pressure, amount, and established. (heat and work)
internal energy).
8. Define CP and Cv. (May/June 2014)
At constant volume (isometric), CV = molar specific heat at constant V

At constant pressure (isobaric), QP = n CP ∆T, CP = molar specific heat at constant P
𝜕𝐻
CP = Specific heat capacity at constant pressure, i.e. 𝐶𝑃 = ( 𝜕𝑇 )
𝑃
𝜕𝑈
CV= Specific heat capacity at constant volume, i.e.𝐶𝑉 = ( 𝜕𝑇 )
𝑉
It can be shown that for a perfect gas: 𝐶𝑃 − 𝐶𝑉 = 𝑅,where R is the gas constant.
The ratio, Cp/Cv =
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9. Give two examples of properties. (May/June 2013)
Temperature, volume, entropy – Examples of reference properties.
Internal energy, enthalpy – Examples of energy properties.
10. Define Helmholtz energy. (May/June 2013,2012)

Helmholtz free energy (A) of a system is defined as A = U – TS
Where, U - Internal energy, T- Temperature, S –Entropy of the system. Since, U, T and S are
characteristic of the system and depend only on its thermodynamic state, Helmholtz free energy is a state
function. Since U and S are both extensive, A also is an extensive property.
11. What are residual properties? (May/June 2012) (Apr/May 2010)

The residual properties are defined as the difference between the thermodynamic property at the
specified temperature and pressure and the property that the substance would have exhibited at the same
temperature and pressure (ideal gas condition).
Properties in the ideal state represented with the superscript id, the residual enthalpy (HR) and residual
entropy (SR) are defined as
HR = H –Hid
SR = S - Sid
12. What are fundamental property relations? (May/June 2013) (Apr/May 2010)
The differentials of energy properties form the basis for the derivation of a large number of equations
relating thermodynamic properties. These are developed for systems of constant mass and composition
in which the only external force is the pressure and the process occurring is reversible.
Fundamental property relations

i) Internal Energy, 𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 → (1)
ii) Enthalpy, 𝐻 = 𝑈 + 𝑃𝑉, 𝑑𝐻 = 𝑑𝑈 + 𝑑(𝑃𝑉 ), 𝑑𝐻 = (𝑇𝑑𝑆 − 𝑃𝑑𝑉 ) + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 → (2)
iii) Helmholtz Free Energy, 𝐴 = 𝑈 − 𝑇𝑆, 𝑑𝐴 = 𝑑𝑈 − 𝑑 (𝑇𝑆) = 𝑑𝑈 − 𝑆𝑑𝑇 − 𝑇𝑑𝑆
𝑑𝐴 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 − 𝑆𝑑𝑇 − 𝑇𝑑𝑆
𝑑𝐴 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇 → (3)
iv) Gibbs Free energy, 𝐺 = 𝐻 − 𝑇𝑆, 𝑑𝐺 = 𝑑𝐻 − 𝑑(𝑇𝑆) = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇
𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 → (4)
13. What are three means by which the second virial coefficient can be determined? (Apr/May 2010)
The second virial coefficient can be determined by,
(i) Kinetic theory
(ii) Equations of state
(iii) Physical interpretation.
14. Define-volume expansivity and isothermal compressibility. (Apr/May 2011)

The volume coefficient of expansion (β) and coefficient of isothermal compressibility (κ) are two other
measurable quantities like heat capacities at constant pressure and constant volume. They are defined as
1  V  1  V 
   ,    
V  T  P V  P T
8
By introducing wherever possible, volume coefficient of expansion (β) and coefficient of isothermal
compressibility (κ), the resulting relationships get fully expressed in terms of measurable quantities.
15. How do you relate the Van der Waals constants to the critical properties? (May/June 2009) (Apr/May
2011)
Van der waals equation is used to explain the P-V-T behavior of real gases.
 a 
 P  2 V  b   RT
 V 
Where a and b are called van der waals constants.
This equation is cubic in volume and below the critical temperature, there are three real roots. The
largest is the vapour volume and the smallest the liquid volume. The intermediate root has no physical
significance. When P is the saturation pressure, the smallest and the largest roots correspond to molar
volumes of saturated liquid and saturated vapour respectively.
8a RT a
VC  3b ; TC  ; PC  C  2
27 Rb 2b 9b
Van der waals constant is expressed in terms of critical properties
2
27 R 2TC RTC
a ; b
64 PC 8 PC
16. Define system.(Nov/Dec 2009)

A system is a region in which the process occurs. (eg) reaction vessel, distillation column.
17. Define system and surroundings. (Nov/Dec 2009)

The part of the universe outside the system and separated from the system by boundaries is called
surroundings.
18. What is physical significance of virial coefficients? (Apr/May 2008)

 Virial coefficients are functions of temperature only (for a given gas).
 virial coefficients can be given physical interpretation.
 The virial coefficients account for the molecular interactions.
The two sets of virial coefficients are related as:
B C  B2
B'  , C' 
RT RT 2
19. What is compressibility factor? (Apr/May 2008)

Compressibility factor (Z) is defined as the ratio of the volume of a real gas (V) to the volume if the gas
behaved ideally at the stated temperature and pressure (RT/P). Virial equations express the
compressibility factor of a gas or vapor as a power series expansion in P or 1/V.
PV
Z  1  B' P  C ' P 2  D' P 3  ....
RT
PV B C D
Z  1   2  3  .....
RT V V V
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20. State the law of corresponding states and explain its significance. (Nov/Dec 2008)
Law of corresponding states: All gases when compared at the same reduced temperature and reduced
pressure, have approximately the same compressibility factor and all deviate from the ideal behavior to
the same extent. Z  f (Tr , Pr )
Significance: generalized compressibility charts are made correlating the P-V-T behavior of all fluids,
based on the principle of corresponding states.
21. What is control volume? (Nov/Dec 2008)

For a control volume, the law of conservation of mass may be written as:
 Rate of accumulati on of mass   Net rate of mass out 
  +   = 0
 Within the control volume   by the flowing streams 
dm
 ( uA)  0
dt
For steady –state flow process, there is no accumulation of mass within the control volume, hence
dm/dt=0 then above equation becomes, ( uA)  0
22. Show that the Joule –Thomson coefficient is zero for ideal gases. (May/June 2007)
RT
For ideal gases: PV  RT  V  , Differentiate w.r.to temperature at constant pressure
P
 V  R
  
 T  P P
V 
Joule Thomson coefficient: C p  T   V
 T  P
V 
Substitute 
R
  in above equation which gives
 T  P P
R
C p  T    V
P
TR RT
C p   0
P P
 0
Hence, Joule Thomson coefficient is zero for ideal gases.
23. State first law of thermodynamics. (May/June 2006)

The law states that change in internal energy (dU) in any system is equal to the heat added to the system
(dQ) minus the work done by the system (dW).
dU  dQ  dW
24. State second law of thermodynamics. (May/June 2006)
The change in entropy (dS) during any change in a system is equal to the heat entering the syatem (when
the change is performed reversibly) divided by the absolute temperature, T.
dQrev
dS 
T
10
Entropy of an isolated system always increases (dS > 0).
The statements for the first and second laws of thermodynamics can be combined: The energy of the
universe is conserved whereas the entropy is increasing.
25. Define a closed system with one example. (Nov/Dec 2003)

Systems that can exchange energy with the surroundings but which cannot transfer matter across the
boundaries are known as closed systems. (eg) batch reactor, power and refrigeration cycles
26. Define an open system with one example.(Nov/Dec 2003)

Systems that can exchange both energy and matter with their environment. (eg) compressor, pump and
heat exchanger.
27. Define Clausius inequality.

In a cyclic operation, the sum of the dQ/T terms around a complete cycle is less than or equal to zero
depending on whether the process is irreversible or reversible.
dQ
 T 0
28. Define the term: Intensive property.
An intensive property is independent of the size of the system. (eg) pressure, temperature and density are
intensive properties.
29. Define the term: Extensive property.

Extensive properties depend on the quantity (or extent) of matter specified in the system. (eg) Mass and
volume are extensive properties.
30. State the commonly used equation for equations of state.

(i) Van der waals equation
(ii) Redlich –Kwong equation
(iii) Redlich-Kwong-Soave equation
(iv) Peng-Robinson equation
(v) Benedict –Webb-Rubin equation
(vi) Virial equation
31. Define equilibrium state.

A system is said to be in a state of equilibrium if the properties are uniform throughout and they do not
vary with time. A system is in
(i) Thermal equilibrium: when no heat exchange occurs within the system & temperature is uniform
throughout.
(ii) Mechanical equilibrium: pressure is uniform.
32. Define triple point of water.

The temperature at which the solid, liquid and vapor phases of water coexist in equilibrium and it is
assigned as value of 273.15 K.
33. State Avogadro’s hypothesis.
11
Avogadro’s hypothesis states that gases containing the same number of molecules occupy the same
volume at same temperature. That is, the number of molecules in one mole of any substance is constant
and it is called the Avogadro Number (N A)
NA = 6.022 x 1023 per mole
34. Mention the application of equation of state?
Equation of state is applicable to gas with very small pressure or very high temperature. With increase in
pressure the intermolecular force of attraction and repulsion increases, and also the volume of the
molecules becomes appreciable compared to the gas volume. Under such condition real gas equations
are to be used.
35. State Hess’s law.
The net heat evolved or absorbed in a chemical reaction is the same whether the reaction takes place in a
single step or in a series of steps.
PART B
1. Derive Maxwell equations and also mention the applications. (13)(APR/MAY
2017,2010,12,13,14) (Narayanan K.V“A Text Book of Chemical Engineering
Thermodynamics” Page No. 192-194)
2. Derive the residual property equation for Gibbs energy, volume, enthalpy and entropy. (13)
(MAY 2010,12,13) (Narayanan K.V“A Text Book of Chemical Engineering Thermodynamics”
Page No. 237-240)
3. (i) Show that ideal gases Cp – Cv = R (4) (MAY 2007) (Narayanan K.V“A Text Book of
Chemical Engineering Thermodynamics” Page No. 208)
(ii) Prove that [dcp/dp]T = -T [d2v / dT2]P. (6) )(MAY 2008,09) (Narayanan K.V“A Text Book of
Chemical Engineering Thermodynamics” Page No. 210-211)
4. Calculate the pressure developed by 1 kmol of gaseous ammonia contained in a vessel of 0.6m3
capacity at a constant temperature of 473 K by the following methods:
(i) Using the ideal gas equation
(ii) Using the vander Waals equation given that
a= 0.4233 Nm4/mol2 ;
b=3.73 x 10-5 m3/mol
(iii) Using the Redlich – Kwong equation given that Pc=112.8 bar; Tc=405.5K
(Apr/May 2010) (Narayanan K.V“A Text Book of Chemical Engineering
Thermodynamics” Page No.73 )
5. Show that
 P   U  (May/June 2009)
(i) T  P 
 T v  V T
 CP    2V 
(ii)    T  2  (Nov/Dec 2009,2008)(Apr/May 2011)
 P T  T  P
 CV    2P 
(iii)    T  2  (Nov/Dec 2008) (Apr/May 2011)
 V T  T V
(Narayanan K.V“A Text Book of Chemical Engineering Thermodynamics” Page
No.210-211)
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6. How is Joule-Thomson coefficient evaluated from P-V-T information? And show that the
Joule-Thomson coefficient is zero for ideal gases. (Narayanan K.V“A Text Book of Chemical
Engineering Thermodynamics” Page No.214-216)
PART-C
1. Deduce from fundamentals, the first law of thermodynamics for flow process. (Apr/May 2017)
(Narayanan K.V“A Text Book of Chemical Engineering Thermodynamics” Page No. 30-32)
2. What are different types of thermodynamic diagrams? Explain the method of construction of
any two thermodynamic diagrams. (May/June 2014) (Narayanan K.V“A Text Book of
Chemical Engineering Thermodynamics” Page No. 240-245)
3. Derive the relationship between entropy and heat capacity. (MAY 2009) (Narayanan K.V“A
Text Book of Chemical Engineering Thermodynamics” Page No.197-199)
4. Develop equations for evaluating the change in internal energy and change in enthalpy for
process involving ideal gases. (Narayanan K.V“A Text Book of Chemical Engineering
Thermodynamics” Page No.200-201)
13
UNIT II - SOLUTION THERMODYNAMICS
PART A
1. What is mass and molar concentration? (Apr/May 2017)
Mass concentration is defined as the mass of a constituent divided by the volume of the mixture. The
mass concentration of a component in a mixture can be called the density of a component in a mixture.
Molar concentration is defined as the amount of a constituent (usually measured in moles ) divided by
the volume of the mixture.
2. Define chemical potential. What is its physical significance? (Apr/May 2017, 2015) (May/June
2013,2012,2009,2007)(Nov/Dec 2010)
Chemical potential is used as an index of chemical equilibrium in the same manner as temperature and
pressure are used as indices of thermal and mechanical equilibrium. The chemical potential μ i of
component I in a solution is same as its partial molar free energy in the solution, G i. That is, chemical
potential of a component i in a solution can be defined as,
 G t 
i  Gi   

 i T , P,n
n
j
3. Differentiate between Clapeyron and Clausius-Clapeyron equations. (May/June 2016) (Apr/May

2011,2010)
Clapeyron equation: The Clapeyron equation predicts the dependence of equilibrium pressure on
temperature when two phases of a given substance coexist. It is given by
dP H

dT TV
Where H and V are the enthalpy and volume change accompanying a phase change.
Clausius-Clapeyron equation: If the temperature is not too near the critical point, the volume of the
liquid is small in comparison with the volume of vapour. The volume change accompanying
vapourization V =VG-VL is therefore approximately equal to VG, the molar volume of vapour.
dP H

dT TVG
The vapour pressure in regions well below the critical point is relatively small so that the vapor can be
assumed to behave as an ideal gas. The molar volume, VG, can now be replaced by RT/PS
So the above equation becomes
dP S H d ln P S H
 PS 2
or 
dT RT dT RT 2
This equation is known as Clausius-Clapeyron equation.
4. What is meant by partial molar property?(May/June 2016) (Apr/May 2011,2008)(Nov/Dec 2010,2009)

Partial molar property of a particular component in a mixture measures the contribution of that
component to the mixture property. The partial molar property M i of the component i in the solution is
defined as
 nM   M t 
M i      
 ni T , P ,n ji  ni T , P,n ji
14
Mt is the total value of any extensive thermodynamic property of a solution, n is the total number of
moles and M is the molar property of the solution. ni denotes the number of moles of component i in the
solution.
5. Distinguish between molar volume and partial molar volume. Does the partial molar volume of a
substance vary with concentration of the substance in the solution? (Apr/May 2015)
Molar volume: consider an open beaker containing a huge volume of water. Assume that one mole of
water is added to it. The volume increases by 18 x 10-6 m3, which is the molar volume of pure water.
Partial Molar volume: if the same amount of water is added to a large amount of pure ethanol taken in
a beaker, the increase in volume will be approximately 14 x 10-6 m3, which is the partial molar volume of
water in pure ethanol.
The difference in the increase in volumes can be explained thus: the volume occupied by a given number
of water molecules depends on the molecules surrounding them. When water is mixed with a large
volume of alcohol, there is so much alcohol present that each water molecule is surrounded by pure
ethanol.
Yes. The partial molar volume of a substance varies with concentration of the substance in the solution.
6. State Raoult’s law, show that it is a simplified form of Lewis Randell rule. (May/June 2014)
Raoult’s law states that the partial pressure of a component in vapor phase is equal to the product of
liquid phase mole fraction and pure component vapor pressure.
𝒑̅𝒊 = 𝒙𝒊 𝑷𝑺𝒊
Lewis Randall rule is applicable to ideal liquid solutions which states that fugacity (𝑓𝑖 ) of each
constituent is directly proportional to the number of moles of the constituent in the solution.
𝒇̅𝒊 = 𝒙𝒊 𝒇𝒊
7. What are excess properties and give its significance? (May/June 2014)(Nov/Dec 2009)
For real liquid solutions, the molar excess property is the departure function which quantifies the
deviation from ideal solution property.
The excess property, ME, is defined as the difference between an actual property and the property that
would be calculated for the same temperature, pressure and composition by the equations for an ideal
solution.
M E  M  M id
M- molar property of the solution
Mid – property of an ideal solution under the same conditions.
ME – excess property
8. State Gibbs Duhem equation.(Nov/Dec 2013) (May/June 2006)

At constant temperature and pressure, the property Mt of the solution is the sum of the partial molar
properties of the constituents, each weighted according to the number of moles of the respective
constituents.
M t  ni M i
9. How is the activity coefficient related to the excess free energy? (May/June 2012,2007) (Apr/May 2011)
The most useful excess property is the partial molar excess Gibbs free energy (G E) which can be directly
related to the activity coefficients.
G E  RT  xi ln  i
15
  (nG E RT ) 
ln  i   
 ni T , P ,n j
10. What do you mean by acentric factor? (Apr/May 2011)
For simple fluids, temperature equal to 7/10 of the critical temperature, the reduced vapor pressure
closely follows the following empirical result:
PS 1 T
 at  0.7
PC 10 TC
S
Where P is the vapor pressure. Pitzer defined the acentric factor in terms of the reduced vapour
pressure at a reduced temperature of 0.7 as
 PS 
  1.00  log  
 PC TR 0.7
For simple fluids, the acentric factor = 0; for more complex fluids, the acentric factor > 0.
11. What are the characteristics of an ideal solution? (Apr/May 2011,2008)

(i) There is no volume change when the components are mixed together to form an ideal solution.
(ii) If a mixture of two liquids is to behave ideally, theoretical considerations reveal that the two
types of molecules must be similar.
12. State Gibb’s theorem. (Apr/May 2010)
Except for volume all other partial molar property of a species in an ideal gas mixture is equal to the
corresponding molar property of the species as a pure ideal gas at a temperature same as that of the
mixture, but at a pressure equal to its partial pressure in the mixture.
13. Define fugacity coefficient. (Apr/May 2010)

The ratio of fugacity to pressure is referred to as fugacity coefficient and is denoted by  . It is
dimensionless and depends on nature of the gas, the pressure, and the temperature.
f

P
14. How is entropy change in an irreversible process determined? (Apr/May 2010)
The entropy change in an irreversible process occurring between any two states would be the same as the
entropy change in a reversible process occurring between them. Thus, the entropy change in any
irreversible process can be evaluated by devising an imaginary reversible process for accomplishing the
same change and calculating the entropy change in the latter.
15. Define the term activity coefficient. (Apr/May 2011) (May/June 2006)
Activity coefficients measure the extent to which the real solution departs from ideality. Activity
coefficient of the component i in the solution is denoted by γi and is defined by the following
relationship.
f i   i xi f i 0
Where f i is the fugacity in the standard state. For ideal solutions  i =1.
0
16
16. What is the effect of temperature on the activity coefficient of a component in a solution? (May/June
2009)
Effect of temperature on activity coefficient is given by
  ln  i  H H
   i 2 i
 T  P RT
The term ( H i  H i ) is the partial heat of mixing of component i from its pure state to the solution of
given composition both in the same state of aggregation and pressure. For gaseous mixtures, this term is
negligible at low pressures.
17. What is the effect of pressure on the activity coefficient of a component in a solution? (May/June 2009)
Effect of pressure on activity coefficient is given by
  ln  i  V  Vi
   i
 P T RT
The molar volumes Vi and Vi correspond to the particular phase under consideration. For liquid
solutions, the effect of pressure on activity coefficients is negligible at pressures below atmospheric. For
gaseous mixtures, activity coefficients are nearly unity at reduced pressures below 0.8.
18. What is a heat pump? (Nov/Dec 2009)

A heat pump is a thermodynamic system operating in a cycle that removes heat from a low temperature
body and delivers it to a high temperature body. External energy in the form of work is necessary to
accomplish this.
19. Define fugacity for a real gas. (Apr/May 2008)(Nov/Dec 2008)

Fugacity is used in the study of phase and chemical reaction equilibria involving gases at high pressures.
For real gas, pressure is replaced by an ‘effective pressure’ or fugacity f of the gas.
dG  RTd ln f 
20. Define fugacity coefficient for a real gas. (Apr/May 2008)(Nov/Dec 2008)
Fugacity coefficient for a real gas is given by the following relation,
P
G  G 0  RT ln 0  RT ln 
P
Free energy of a real gas=free energy of an ideal gas + RT ln  . The quantity RT ln  ,therefore,
expresses the entire effect of intermolecular interaction.
17
21. What is an inversion point? (Nov/Dec 2008)
At any given pressure, the joule-Thomson coefficient is positive only within a temperature range that is
between the upper and lower inversion temperatures. Only within these temperatures a gas cools on
throttling.
22. Define COP of refrigerator. (Nov/Dec 2008)

The coefficient of performance (COP) is defined as the ratio of heat transferred from low temperature
reservoir (Q2) to the work-input (W). For refrigerator,
Q
 2
W
23. Define COP of pump. (Nov/Dec 2008)
The COP is defined as the ratio of heat rejected (Q 1) to the work-input (W).
For heat pump,
Q
 1
W
24. Define the term activity.
Activity or relative fugacity is defined as the ratio of fugacity to fugacity in the standard state. It finds
wide application in the study of homogeneous chemical reaction equilibria involving solids and liquids.
Activity is denoted by ‘a’.
f
a
f0
25. What are ideal solutions?
A solution in which the partial molar volumes of the components are the same as their molar volumes in
the pure state is called an ideal solution.
26. State Lewis fugacity rule. (Nov/Dec 2013)

It states that the fugacity of a component in an ideal solution is directly proportional to the mole fraction
of the component in the solution.
f i  yi f i
Lewis fugacity rule is valid for systems where the intermolecular forces in the mixture are similar to
those in the pure state.
27. State Henry’s law.
Partial pressure or fugacity is directly proportional to the concentration in the liquid or its mole fraction,
the proportionality constant.
pi  xi ki Or f i  xi ki
pi - Partial pressure of the solute
xi - Mole fraction in the solution
k i - Proportionality constant (or) Henry’s law constant
18
28. Define non -ideal solution.
A solution, any of whose components does not obey Raoult’s law is known as non-ideal solution. Even
non –ideal solutions exhibit a common form of ideal behavior over a limited concentration range where
the fugacity (or, the partial pressure) is directly proportional to the concentration in the liquid.
29. State lewis Randall rule.

Lewis Randall rule is applicable to ideal liquid solutions which states that fugacity ( 𝑓𝑖 ) of each
constituent is directly proportional to the number of moles of the constituent in the solution.
𝒇̅𝒊 = 𝒙𝒊 𝒇𝒊
30. Define partial molar volume.

Partial Molar volume: if the same amount of water is added to a large amount of pure ethanol taken in
a beaker, the increase in volume will be approximately 14 x 10 -6 m3, which is the partial molar volume of
water in pure ethanol.
The difference in the increase in volumes can be explained thus: the volume occupied by a given number
of water molecules depends on the molecules surrounding them. When water is mixed with a large
volume of alcohol, there is so much alcohol present that each water molecule is surrounded by pure
ethanol.
31. Mention the application of Gibbs Duhem equation.
Gibbs-Duhem equation can be used for the calculation of
(i) a partial molar quantity of a binary mixture from measurements of the composition dependence of the
corresponding total molar quantity,
(ii) the partial molar quantity of a component, say 1, of a binary mixture from measurements of the
composition dependence of the corresponding partial molar quantity of component 2, and
(iii) the partial vapor pressures from measurements of the liquid-phase composition dependence of the
total vapor pressure.
32. Define Clausius-Clapeyron equations.
Clausius-Clapeyron equation: If the temperature is not too near the critical point, the volume of the
liquid is small in comparison with the volume of vapour. The volume change accompanying
vapourization V =VG-VL is therefore approximately equal to VG, the molar volume of vapour.
dP H

dT TVG
The vapour pressure in regions well below the critical point is relatively small so that the vapor can be
assumed to behave as an ideal gas. The molar volume, VG, can now be replaced by RT/PS
So the above equation becomes
dP S H d ln P S H
 PS 2
or 
dT RT dT RT 2
This equation is known as Clausius-Clapeyron equation.
33. State the Characteristics of Entropy.

1. It increases when the heat is supplied irrespective of the fact whether temperature changes or not.
2. Whether temperature changes or not the entropy decreases when heat is rejected.
3. In all the adiabatic processes, the entropy remains constant.
34. State conditions of Lewis fugacity rule.
19
Lewis fugacity rule is valid
(i) At low pressures when the gas phase behaves ideally
(ii) At any pressure if the component is present in excess
(iii) If the physical properties of the components are nearly the same
(iv) At moderate and high pressures, the Lewis-Randall rule will give incorrect results if the
molecular properties of the components are widely different and the component under
consideration is not present in excess.
PART B
1. Derive an expression for fugacity and fugacity coefficient of pure species.(APR/MAY

2017,2007) (Narayanan K.V“A Text Book of Chemical Engineering Thermodynamics” Page
No.225 – 228)
2. Discuss the importance of Gibbs-Duhem equation and explain its various forms. Explain the
applications of Gibbs-Duhem equation. (MAY 2017, 2010,12,13,14) (Narayanan K.V“A Text
Book of Chemical Engineering Thermodynamics” Page No.283-285)
3. Derive the Lewis / Randell rule as applicable to ideal solutions. (MAY 2010) (Narayanan
K.V“A Text Book of Chemical Engineering Thermodynamics” Page No.271-272)
4. At 300 K and 1 bar, the volumetric data fo r a liquid mixture of benzene and cyclohexane are
represented by 𝑉 = 109.4 × 10−6 − 16.8 × 10−6 𝑥 − 2.64 × 10−6 𝑥 2 , where x is the mole
fraction of benzene and V has the units of 𝑚3 ∕ 𝑚𝑜𝑙. Find the expressions for the partial molar
volumes of benzene and cyclohexane. (May/June 2014,2013) (Narayanan K.V“A Text Book of
Chemical Engineering Thermodynamics” Page No.262-263)
5. Derive the expressions for the effect of temperature and pressure on activity coefficient.
(Nov/Dec 2013) (Narayanan K.V“A Text Book of Chemical Engineering Thermodynamics”
Page No.236 - 237)
6. The enthalpy of a binary liquid mixture containing components 1 and 2 at 298 K and 1.0 bar is
given by
H= 400x1 + 600x2 + x1x2(40x1 + x2)
where H is in J/mol, Determine
(i) Pure component enthalpies
(ii) Partial molar enthalpies (Apr/May 2015,2011) (Narayanan K.V“A Text Book of
PART-C
1. Explain the methods by which fugacity for a pure component is calculated. (MAY
2010,12)(Narayanan K.V“A Text Book of Chemical Engineering Thermodynamics” PageNo.228-234)
2. Derive the expressions for the effect of temperature and pressure on fugacity coefficient.
(Nov/Dec 2013) (Narayanan K.V“A Text Book of Chemical Engineering Thermodynamics”
Page No.227-228)
3. Find the van Laar constants for the binary system benzene (1) – ethanol (2) using the
following data:
x1 0.1 0.3 0.45 0.7 0.9
S
P1 kPa 73.31 68.64 63.98 67.98 81.31
S
P2 75.98 69.64 67.98 69.31 79.98
kPa
20
(May/June 2016)
(Narayanan K.V“A Text Book of Chemical Engineering Thermodynamics” Page No.389)
4. Two substances A and B are known to form ideal liquid solutions. A vapour mixture
containing 50% (mol) A and 50% (mol) B is at 311 K and 101.3 kPa. This mixture is
compresses isothermally until condensation occurs. At what pressure, does condensation occurs
and what is the composition of the liquid that forms? The vapour pressures of A and B are 142
kPa and 122 kPa respectively. (May/June 2016) (Narayanan K.V“A Text Book of Chemical
Engineering Thermodynamics” Page No.386)
21
UNIT III - PHASE EQUILIBRIA
PART A
1. Define the term Phase equilibria. (Apr/May 2017)
The equilibrium state of a closed system is that state for which the total Gibbs energy is a minimum with
respect to all possible changes at the given T and P.
2. In liquid –liquid equilibrium curve, define plait point with neat sketch. (Apr/May 2017)
The Plait Point P is the intersection of the raffinate-phase and extract-phase boundary curves. At
this point, the equilibrium phases become coincident and no separation can be made at that point.
3. Distinguish between bubble point and dew point temperature. (May/June 2016, 2012) (Apr/May
2011,2008)
S.No Bubble point temperature Dew point temperature
1 The first bubble of vapour is The first drop of condensate is formed on

produced from the liquid on heating cooling a vapour at constant pressure.
at a constant pressure.
2 At the bubble point the liquid has the The vapour in equilibrium with the liquid
same composition as the original at the dew point has the same composition
mixture. as the original mixture.
3 At bubble point, ∑yi = ∑ki xi = 1 At dew point, ∑ xi = ∑ yi / ki = 1
4. What is an azeotrope? Under what conditions do azeotropes generally form? (May/June 2016, 2014)
An azeotrope is a mixture of two or more liquids whose proportions cannot be altered by
simple distillation. This happens because, when an azeotrope is boiled, the vapor has the same
proportions of constituents as the unboiled mixture. Because their composition is unchanged by
distillation, azeotropes are also called constant boiling mixtures.
22
5. What is critical solution temperature? (Apr/May 2015) (May/June 2012)
The point P gives the critical solution temperature. This point represents the last of the tie lines where the
A-rich and B-rich phases become identical.
6. Write down the equation for solving general VLE problem. (Apr/May 2015)(Nov/Dec 2008)
Vapour liquid equilibrium (VLE) data are essential for many engineering calculations, especially in the
design and analysis of separation operations such as distillation, absorption, etc. The fundamental
relationship in the study of vapor liquid equilibrium is given by,
̅𝑖 𝑃 = 𝛾𝑖 𝑥𝑖 𝑓𝑖𝑜 .
𝑦𝑖 𝜙
7. What is Poynting correction? (May/June 2014)

For a pure fluid in vapor–liquid equilibrium, the vapor phase fugacity is equal to the liquid phase
̅𝑖 𝑃 = 𝛾𝑖 𝑥𝑖 𝑓𝑖𝑜 .At
fugacity. The fundamental relationship in the study of vapour-liquid equilibrium is 𝑦𝑖 𝜙
𝑉𝑖 (𝑃−𝑃𝑖𝑆
pressures above the saturation pressure, the liquid phase fugacity is 𝑓𝑖𝑜 = 𝜙𝑖𝑆 𝑃𝑖𝑆 𝑒𝑥𝑝 [ ]. When
𝑅𝑇
𝑉𝑖 (𝑃−𝑃𝑖𝑆
̅𝑖 𝑃 = 𝛾𝑖 𝑥𝑖 𝜙𝑖𝑆 𝑃𝑖𝑆 𝑒𝑥𝑝 [
this equation is substituted in the first equation, we get, 𝑦𝑖 𝜙 ] . The
𝑅𝑇
exponential term represents the Poynting correction factor and is usually near 1.0 unless pressures are
very high.
8. What is the general criteria for phase equilibrium for heterogeneous multicomponent system?(Nov/Dec
2013) (May/June 2013)
When a system consisting of several components distributed between various phases is in
thermodynamic equilibrium at a definite temperature and pressure, the chemical potential of each
component is the same in all the phases.
If they are different, the component for which such a difference exists will show a tendency to pass from
the region of higher to the region of lower chemical potential.
Thus the equality of chemical potential along with the requirement of uniformity of temperature and
pressure serves as the general criterion of thermodynamic equilibrium in a heterogeneous
multicomponent system.
T = constant; P = constant
i  i  ...  i for i = 1,2,3,…..C
23
9. What are bubble point and dew point temperatures? (May/June 2013)
Bubble point temperature: Bubble point temperature is the one at which the first bubble of vapour is
produced from the liquid on heating at a constant pressure.
Dew point temperature: Dew point temperature is one at which the first drop of condensate is formed
on cooling a vapour at constant pressure.
10. What is the fugacity criterion for phase equilibrium? (Apr/May 2011) (Apr/May 2010)
General fugacity criterion for phase equilibrium is given by
T = constant; P = constant
f i  f i   ....  f i  for i = 1,2,3,…..C
Fugacity is a more useful property than chemical potential for defining equilibrium since it can be
expressed in absolute values, whereas chemical potential can be expressed only relative to some arbitrary
reference state. This equation is widely used for the solution of phase equilibrium problems.
11. Brief on bubble point and dew point pressures. (Apr/May 2011) (Nov/Dec 2008)
To find the bubble point pressure, assume various values of pressure and get the k i values at this
pressure. Calculate yi = kixi. if the assumed pressure is correct then ∑yi = ∑ki xi = 1
To find the dew point pressure, pressure is assumed arbitrarily and ki is determined. Then, xi=yi/ki
At the dew point, ∑ xi = ∑ yi / ki = 1.
12. What is the criterion for liquid-liquid equilibrium? (Apr/May 2010)

 
f i  f i  for all i=1,2,…….n, α and β are two liquid phases.
13. Define lower critical solution temperature and upper critical solution temperature. (Apr/May 2010)
The curves FC and GD eventually merge to a single point and the two liquid phases become identical.
The temperature at which this occurs is known as the upper critical solution temperature (UCST). For
pressures above this critical condition, the three phase equilibrium conditions do not exist.
24
14. What is meant by positive and negative deviations from Raoult’s law? (Apr/May 2010)
Positive deviation from ideality results when the actual partial pressure of each constituent is greater
than it should be if Raoult’s law were obeyed. It is present in solutions in which intermolecular forces
between like molecules are stronger than those between unlike molecules.
(eg) benzene-cyclohexane, water-ethanol, O2-N2.
Negative deviation from ideality results when the partial pressures are less than those given by Raoult’s
law. At molecular level, negative deviation reflects stronger intermolecular forces between unlike
molecules than between like pairs of molecules.
(eg) chloroform-acetone, HCL-water, chloroform-benzene.
15. How does one mathematically express the molar change in enthalpy (dh) for a multicomponent system?
(Apr/May 2010)
dP
dh  TV
dT
Where
V - volume change accompanying phase rule
dP- change in pressure
dT-change in temperature
16. State Gibb’s phase rule. (Nov/Dec 2010)

F  C    2 . This equation is known as Gibbs phase rule.
F-Number of degrees of freedom
 -The number of phases in equilibrium
C- Number of components constituting the system.
17. List the criteria for phase equilibrium. (Nov/Dec 2010)

The criteria of internal thermal and mechanical equilibrium are that the temperature and pressure be
uniform throughout the system.
(i) Constant U and V : dSU ,V  0
(ii) Constant T and V: dAT ,V  0
25
(iii) Constant P and T: dGT , P  0
18. How do you predict the low pressure VLE data for a binary system using the excess Gibbs free energy
models? (May/June 2009)
Redlich-kister method is used to test the consistency of experimental data when the activity coefficient
value over the entire concentration range is available. It is based on the excess free energy of mixing
which is the difference between the free energy of mixing of a real solution and that of an ideal solution.
G E  RT  xi ln  i
For a binary solution, it can be written as
G E  RT  x1 ln  1  x2 ln  2 
19. What is an azeotrope? (May/June 2009)
An azeotrope is a mixture of two or more liquids whose proportions cannot be altered by
simple distillation. This happens because, when an azeotrope is boiled, the vapor has the same
proportions of constituents as the unboiled mixture. Because their composition is unchanged by
distillation, azeotropes are also called constant boiling mixtures.
20. How many types of azeotropes are there? (May/June 2009)

There are two types of azeotropes.
(i) Minimum boiling azeotropes
(ii) Maximum boiling azeotropes.
21. Define equilibrium in terms of chemical potential. (Nov/Dec 2009)

For the system to be in equilibrium with respect to mass transfer, the driving force for mass transfer –the
chemical potential- must have uniform values for each component in all phases.
  dn  0 (At constant temperature and pressure)
i i
22. Define isochoric process. (Nov/Dec 2009)

The relationship between pressure and volume is assumed to be PV n  cons tan t , where n is a constant.
If n   , the process is isochoric (constant volume).
23. Why does immiscibility occur in liquid solutions? (May/June 2009)

The equilibrium state of the system is two phases of a fixed composition corresponding to a temperature.
The compositions of two such phases, however, change with temperature.
24. Define coexistence equation and its applications. (May/June 2009)

The coexistence equation can be used for testing the consistency of vapor-liquid equilibrium data.
dP P y1  x1 

dy1 y1 1  y1 
The above equation is known as the coexistence equation.
26
25. Write the applications of coexistence equation. (May/June 2009)
Applications:
(i) It can be used to calculate any one of the three variables P, x or y if experimentally measured
values of the other two variables are available.
(ii) If all the three variables are experimentally determined, then coexistence equation can be used to
test the consistency of the measured data.
26. State Duhem’s theorem.

For any closed system formed initially from the given masses prescribed chemical species, the
equilibrium state is completely determined when any two independent variables are fixed.
27. Explain about consistency test.

Thermodynamic provides tests for consistency of experimental VLE data, as the VLE measurements are
prone to accuracies.
All the tests are based on Gibbs-Duhem equation written in terms of activity coefficients.
  ln  1    ln  2 
x1    x2  
 x1 T , P  x2 T , P
28. Name the different types of consistency tests for VLE data.
(i) Using slope of lnγ curves
(ii) Using data at the Mid-point
(iii) Redlich-kister method (or) zero order method
(iv) Using the coexistence equation
(v) Using the partial pressure data.
29. Define criterion of stability.

At constant temperature and pressure, the free energy change on mixing ∆G, its first and second
derivatives are all continuous functions of the concentration x and
d 2 G
> 0 at constant T & P.
dx12
30. Define system at equilibrium.
System at equilibrium is defined as one in which there are no driving forces for energy or mass transfer.
That is for a system in a state of equilibrium, all forces are in exact balance.
31. What are the two types of phase equilibrium problems?

(i) The determination of composition of phases which exist in equilibrium at a known temperature
and pressure
(ii) The determination of conditions of temperature and pressure required to obtain equilibrium
between phases of specified compositions.
32. What are the advantages of NRTL equation?
NRTL equation is applicable to partially miscible as well as totally miscible systems. This equation is
also applicable for non ideal solutions and especially partially miscible systems.
27
33. What is bubble point temperature?
Bubble point temperature is the one at which the first bubble of vapour is produced from the liquid on
heating at a constant pressure.
34. What is dew point temperature?

Dew point temperature is one at which the first drop of condensate is formed on cooling a vapour at
constant pressure.
35. Define zero order method.

This method is used to test the consistency of experimental data when the activity coefficient value over
the entire concentration range is available. It is based on the excess free energy of mixing which is the
difference between the free energy of mixing of a real solution and that of an ideal solution.
PART B
1. Construct the P-x-y diagram for the cyclohexane(1)-benzene (2) system at 313 K the vapour
pressures are P1S =24.62 kPa and P2S = 24.41 kPa. The liquid-phase activity coeffiients are
given by ln  1  0.458x22 , ln  2  0.458 x12 . (Apr/May 2017, 2015) (May/June 2012) (Narayanan
K.V“A Text Book of Chemical Engineering Thermodynamics” Page No.356)
2. Explain the phase equilibria in single component systems. (May/June 2013) (Narayanan K.V“A
Text Book of Chemical Engineering Thermodynamics” Page No.315-316)
3. (i) Describe the methods used for testing the thermodynamic consistency of experimentally
determined vapor-liquid equilibrium data for binary systems. (MAY 2007,11) (Narayanan
(ii) Compare Dew point and bubble point temperature. (4) (Apr/May 2007,11) (Narayanan
4. Explain the liquid/liquid solubility diagram for liquid liquid equilibrium (10) (MAY 2007,11)
(Narayanan K.V“A Text Book of Chemical Engineering Thermodynamics” Page No.381-383)
5. A binary system, (i) benzene (ii) ethyl benzene obeys the Raoult’s law and at vapour pressures
are given by the Antoine equations
2788.51
ln 𝑃1𝑆 = 13.8858 −
𝑇 − 52.41
3279.47
ln 𝑃2𝑆 = 14.0045 −
𝑇 − 60.00
where P is in kPa and T is in K. Construct the p-x-y at 373K and T-x-y at 101.3 kPa. (May/June
2014) (Narayanan K.V“A Text Book of Chemical Engineering Thermodynamics” Page No.337)
6. Ethanol-water mixture forms an azeotrope boiling at 351.4K under a pressure of 101.3kPa and its
composition is 89.4% (mol) ethanol. The vapour pressures of ethanol and water at 351.4K are 100 kPa
and 44 kPa respectively. Using Van Laar method and assuming that the ratio of vapour pressures
remains constant. Calculate the composition of the vapor in equilibrium with a liquid containing 80%
ethanol. (May/June 2013) (Narayanan K.V“A Text Book of Chemical Engineering Thermodynamics”
Page No.390)
PART C
28
1. At 750 mm Hg pressure, the A-B azeotrope boils at 65°C and contains 35 mole% of A. The vapor
pressure of A and B are 1000 mm and 800 mm of Hg respectively at 65°C. Calculate the composition of
vapour at this temperature in equilibrium with liquid analyzing 10 mole% of A. what is the total pressure
at this condition? (Apr/May 2017) (class notes)
2. Discuss in detail about Vapour – Liquid Equilibria (VLE) at low pressures. (Narayanan K.V“A Text
Book of Chemical Engineering Thermodynamics” Page No.347-352)
3. Explain in detail about the methods available for calculation of Vapour Liquid Equilibria involving high
pressures. (Narayanan K.V“A Text Book of Chemical Engineering Thermodynamics” Page No.362-364)
4. A vapour mixture containing 18% ethane, 17% propane, 62% isobutene and the rest n-butane is
subjected to partial condensation so that 75% of the vapour is condensed. If the condenser temperature is
300 K, determine the pressure.(May/June 2016) (Narayanan K.V“A Text Book of Chemical Engineering
Thermodynamics” Page No. 391)
29
UNIT IV- CHEMICAL REACTION EQUILIBRIA
PART A
1. When the chemical reaction attains equilibrium? (Apr/May 2017)

The chemical equilibrium state describes concentrations of reactants and products in a reaction taking
place in a closed system, which no longer change with time. In other words, the rate of the forward
reaction equals the rate of the reverse reaction, such that the concentrations of reactants and products
remain fairly stable, in a chemical reaction. Equilibrium is denoted in a chemical equation by the ⇌
symbol.
2. For the gas phase reaction C2H4 + H2O → C2 H5OH the equilibrium constant at 145°C and 1 bar is K=
6.8 x 10-2, how would you calculate the equilibrium constant at 10 atm pressure? (Apr/May 2017)
Solution:
Given data: T =145°C, P= 1 bar, K= 6.8 x 10-2
Equilibrium constant k =? At P = 10 atm.
3. Define equilibrium constant Ke of a chemical reaction. How is it related to Kf and Kp? (May/June 2016)
(Apr/May 2011)(May/June 2007)
Consider the chemical reaction aA  bB  lL  mM
The equilibrium constant Ke for this reaction is defined in terms of the activities of the reactants and the
products as
aLl aMm
Ke  a b
 aivi
a A aB
Where ai is the activity of component i in the reaction mixture and vi is the stoichiometric number of i.
Equilibrium constant in terms of fugacity is given by
K e   f i  i  K f
v
Equilibrium constant in terms of partial pressures is given by

Ke   pi  i
v
For gaseous systems, the relationship between equilibrium constants is given by K  K f  K p .

4. What is reaction coordinate? What is its significance in chemical reaction? (Apr/May 2015)
Reaction coordinate measures the progress of a reaction. It is defined as the degree to which a reaction
has advanced. Reaction coordinate is otherwise known as extent of reaction.
The extent of reaction and number of moles taking part in the reaction are related as,
30
dni
 d
vi
For the initial state of the system, (ie) before the reaction, the value of ε is zero.
5. What is the effect of pressure on equilibrium conversion of a gas-phase chemical reaction? (Apr/May
2015) (Apr/May 2008)
In the case of reaction equilibrium for N 2  3H 2  2 NH3 formation of ammonia will be favored by an
increase in pressure as there is a reduction in the number of moles due to this reaction. When the
composition of the system changes in this manner in response to increase or decrease in pressure, it does
so without changing the equilibrium constant.
6. What is the phase rule for reacting systems? (May/June 2014) (Nov/Dec 2013)
The number of degrees of freedom will be reduced by one for each independent chemical reaction. If r
independent reactions occur in the system, then the phase rule becomes
F=C–п–r+2
7. What is meant by extent of reaction? (May/June 2014)(May/June 2013)(Nov/Dec 2010)

The extent of the reaction measures the progress of the reaction and it is defined as the degree to which a
reaction has advanced. It is denoted by. It is also known as the reaction coordinate. It has the advantage
that the change in the change in the extent of reaction d is the same for each component, whereas the
change in the number of moles is different for different species taking part in the reaction.
𝑑𝑛𝑖
= 𝑑𝜀
𝑣𝑖
8. List the criterion for chemical reaction equilibria. (May/June 2013,2012)

At constant temperature and pressure, the transfer of materials from one phase to another under
equilibrium is found to occur with no change in the free energy.
dGTt ,P  0
The criterion of equilibrium for chemical reaction is given by
 v i i 0
9. How the equilibrium is constant related to the standard free energy change? (May/June 2012)
The standard free energy change G 0 , accompanying the reaction when each of the reactants and the
products is in its standard state.
G 0   RT ln K
The equilibrium constant is determined by the standard free energy change and the temperature.
The standard free energy change depends on the temperature, the specification of standard state for each
component and the number of moles involved in the stoichiometric equation under consideration.
10. Explain the concept of entropy and enthalpy departures. (Apr/May 2011)
The departure functions are defined as the difference between the thermodynamic property at the
specified temperature and pressure and the property that the substance would have exhibited at the same
temperature and pressure (ideal gas condition).
Properties in the ideal state represented with the superscript id, the residual enthalpy (HR) and residual
entropy (SR) are defined as
31
HR = H –Hid
SR = S - Sid
HR and SR are known as enthalpy departure and entropy departure. These represent hypothetical
property changes because a gas cannot be both real and ideal at a given P and T.
11. What is standard Gibbs free energy change of a chemical reaction and how is it related to the equilibrium
constant? (Apr/May 2011)(Nov/Dec 2010,2008) (May/June 2009)
The standard free energy change depends on the temperature, the specification of standard state for each
component and the number of moles involved in the stoichiometric equation under consideration. It is
independent of pressure at equilibrium. Temperature in the standard state is the same as that in the
equilibrium state.
aLl aMm
 i0vi   RT ln a Aa aBb
The left hand side gives the standard free energy change G 0 , accompanying the reaction when each of
the reactants and the products is in its standard state.
G 0   RT ln K
12. Define van’t Hoff equation. (Apr/May 2011) (May/June 2007)

d ln K H 0

dT RT 2
This equation is known as van’t Hoff equation, predicts the effect of temperature on the equilibrium
constant and hence on the equilibrium yield.
H 0 - Standard heat of reaction. If H 0 is negative, ie. if the reaction is exothermic, the equilibrium
constant decrease as the reaction temperature increases. If H is positive, i.e. if the reaction is an
0
endothermic reaction, the equilibrium constant will increase with increase in temperature.
13. State the effect of temperature of Equilibrium constant. (Apr/May 2010)

An increase in temperature will shift the equilibrium state in the direction of absorption of heat. That is,
the equilibrium will shift in the endothermic direction if the temperature is raised, for then, energy is
absorbed as heat.
Similarly, equilibrium can be expected to shift in the exothermic direction if the temperature is lowered,
for then the reduction in temperature is opposed. Thus, an endothermic reaction is favored by an increase
in temperature and an exothermic reaction is favoured by a decrease in temperature.
The effect of temperature on equilibrium constant is quantitatively expressed by van’t Hoff equation.
14. How does the standard heat of reaction related to standard Gibbs-energy change of reaction? (Apr/May
2010)
The standard free energy of the reaction and standard heat of reaction are related to the free energy and
enthalpy of individual species respectively as given below.
G 0  vi Gi0 , H 0  vi H i0
The relationship between standard heat of reaction and standard Gibbs-energy change of reaction is
given by
32
 
 d G 0
RT
   H 0
 
 dT  RT 2
 
15. List down the causes of entropy change in chemical systems. (Apr/May 2010)
In an irreversible process, a decrease in entropy may occur either in the system or in the surroundings.
These statements require only that the sum of the entropy changes of the system and the surroundings
together be positive in an irreversible process like the isothermal expansion of a gas. If the same
expansion were carried out reversibly, the increase in the entropy of the gas will be compensated by a
decrease in the entropy of the surroundings that results because of the withdrawal of heat. If this heat
exchange also were accomplished reversibly, the net change in entropy would be zero.
16. What do you understand by the number of independent reactions in a chemically reacting system?
(Apr/May 2010)
The number of independent reactions that must be considered as the least number that includes every
reactant and product present to an appreciable extent in all phases of the equilibrium system, and
accounts for the formation of each product from the original reactants.
17. How does the dilution of a reaction mixture with an inert gas effect the degree of conversion in a gas
phase reaction? (May/June 2009)
Diluting the reaction mixture with an inert material will increase total number of moles in the reaction
mixture (N). This will result in an increased conversion, if v is positive. That is, if the reaction proceeds
with an increase in the number of moles, presence of inerts in the system will increase the equilibrium
yield.
18. What do you understand by the term “available energy”? (Nov/Dec 2009)
Available energy is the greatest amount of mechanical work that can be obtained from a system or body,
with a given quantity of substance, in a given initial state, without increasing its total volume or
allowing heat to pass to or from external bodies, except such as at the close of the processes are left in
their initial condition. In this definition, the initial state of the body is supposed to be such that the body
can be made to pass from it to states of dissipated energy by reversible processes.
19. Is the Gibbs free energy change of a chemical reaction related to the work done by the system? Give an
example. (Apr/May 2008)
Yes. The value of ∆G in any process is quite definite, no matter under what conditions the process is
carried out, but only the temperature and pressure are constant the free energy change would represent
the maximum net work available from the given change in state.
(eg) The maximum electrical work that could be done by the system undergoing a given change in state
is less than the maximum work, - ∆A, by the expansion work and is measured by the decrease in the
Gibbs free energy, - ∆G.
33
20. How the number of independent reactions in a chemically reacting system is determined?
(i) For each chemical compound present in the system, an equation for its formation reaction from
its elements is written. (F = C – п – r + 2)
(ii) The elements that are not present in the system are eliminated by properly combining the
equations written in step (i).
The number of equations, r that results from the above procedure is equal to the number of
independent chemical reactions occurring.
21. What do you understand by the principle of increase in entropy? (Apr/May 2008)
The principle of increase in entropy with reference to an isolated system means that the only processes
that can occur in an isolated system are those that have an increase in entropy associated with them. The
universe is a perfect example of an isolated system and all naturally occurring processes in the universe
are accompanied by an increase in entropy and are irreversible. Hence we can say that the entropy of the
universe goes on increasing.
22. Give an explanation of the effect of the pressure on a first order reaction. (May/June 2006)
Increasing the pressure on a reaction involving reacting gases increases the rate of reaction. Changing
the pressure on a reaction which involves only solids or liquids has no effect on the rate.
23. Give an explanation of the effect of the temperature on a first order reaction. (May/June 2006)
The fraction of molecules whose kinetic energy exceeds the activation energy increases quite rapidly as
the temperature is raised. This is the reason, all chemical reaction proceed more rapidly at higher
temperature.
24. What reaction conditions affect the equilibrium conversion in chemical reactions?
Temperature, pressure, excess amount of reactants, initial amount of products and inert substances.
25. What is the significance of free energy calculations in the thermodynamic analysis of chemical
reactions?
To find the equilibrium compositions, from free energy calculations, we can find the feasibility of a
reaction.
(i) G 0 < 0, the reaction is promising.
(ii) 0 < G 0 < 40,000 kJ/kmol, the reaction may or may not be possible and needs further study.
(iii) G 0 > 40,000 kJ/kmol, the reaction is very unfavorable.
These guides may be useful as an approximate criterion for ascertaining the feasibility of
chemical reactions.
26. What is quasistatic process? (May/June 2006)

Consider the special case of an interaction of the system A with its surroundings which is carried out so
slowly that A remains arbitrarily close to equilibrium at all times. Such a process is said to be quasistatic
for the system.
dQ=dE +dW
dQ- infinitesimal heat
dE- infinitesimal work
dW – environment
34
27. How you evaluate the entropy changes accompanying chemical reactions?
The entropy changes accompanying chemical reactions are evaluated through the use of absolute
entropies of the various components taking part in the reaction. Let S P denote the sum of the entropies of
the reactants and SR denotes that of the products. Then the entropy change accompanying the reaction by
S  SP  SR
28. What are Giauque functions?

Data for calculation of standard free energy of reactions are sometimes tabulated as Giauque functions.
These are Gibbs free energy functions that vary very slowly with temperature. Two such functions are in
general use – the first is referred to 0 K and the second referred to 298 K. These are written as
GT0  H 00 G 0  H 298
0
0  , 298  T
T T
29. What will happen if the system is not in chemical equilibrium?
If the system is not in chemical equilibrium, the reaction occurring must be irreversible and the total
Gibbs free energy must decrease at constant temperature and pressure.
30. Define heterogeneous reaction equilibria.

In the study of heterogeneous reaction equilibria, we are concerned with a gas phase that is in
equilibrium with a liquid or a solid phase. When the heterogeneous system is in equilibrium we would
have to consider the equilibrium with respect to chemical reactions in the gas phase as well as the phase
equilibria between the components in the gas phase and the liquid or the solid phase as the case may be.
31. What is the effect of presence of inert materials?
Diluting the reaction mixture with an inert material will increase the total number of moles in the
reaction mixture. This will result in an increased conversion if v is positive. That is, if the reaction
proceeds with an increase in the number of moles, presence of inerts in the system will increase the
equilibrium yield. The presence of inerts will decrease conversion if the reaction is accompanied by a
decrease in the number of moles, and the inerts present in the system will have no influence on the
degree of completion if v is zero, if there is no change in the number of moles during a reaction.
32. What is effect of presence of excess of reactants?
When the reactants are not present in stoichiometric proportions, increasing the number of moles of the
excess reactant will result in increase in the number of moles of the products and improved conversion of
the limiting reactant at equilibrium.
33. What is the effect of addition of inert gas at constant volume?

When an inert gas is added to the system in equilibrium at constant volume, the total pressure
will increase. But the concentrations of the products and reactants (i.e. ratio of their moles to the
volume of the container) will not change.
34. What is the effect of addition of inert gas at constant pressure?

When an inert gas is added to the system in equilibrium at constant pressure, then the total volume will
increase. Hence, the number of moles per unit volume of various reactants and products will decrease.
Hence, the equilibrium will shift towards the direction in which there is increase in number of moles of
gases.
35
35. What is the effect of presence of products?
If the initial reaction mixture contained any of the products of the reaction, then the number of moles of
that product formed by the reaction so as to establish equilibrium will decrease. Therefore, the addition
of the products to the original reactant stream decreases the equilibrium conversion.
PART B
1. Methanol is produced by the following reaction: CO(g) + 2H 2(g) →CH3OH(g). The standard
heat of formation of CO(g) and CH3OH(g) at 298 K are -110,500 J/mol and -200,700 J/mol
respectively. The standard free energies of formation are -137,200 J/mol and -162,000 J/mol
respectively. Calculate the standard free energy change and determine whether the reaction is
feasible at 298K. Determine the equilibrium constant at 400 K assuming that the heat of
reaction is constant. (May/June 2015, 2012,13) (Narayanan K.V“A Text Book of Chemical
Engineering Thermodynamics” Page No.442)
2. Derive the effect of pressure and temperature on the equilibrium constants. (May/June
2012,13)(Nov/Dec 2008) (Narayanan K.V“A Text Book of Chemical Engineering
3. (i) Derive the equilibrium criteria for homogeneous chemical reactions. (8) (Nov 2009,10)
(Narayanan K.V“A Text Book of Chemical Engineering Thermodynamics” Page No.402-404)
(ii) Explain the factors affecting equilibrium conversion (8) (Nov 2009,10) (Narayanan
4. Prove that Ka = Kf = Kp with example. (Nov/Dec 2013) (Narayanan K.V“A Text Book of
5. A gaseous mixture containing 30% CO, 50% H2 and the rest inert gas is sent to a reaction
chamber for methanol synthesis. The following reaction occurs at 635 K and 310 bar.
CO (g) + 2H2 (g) → CH3OH (g)
Assuming that the gas mixture behaves as an ideal solution, calculate the percent conversion of
CO given that K f = 5X 10-5 and Kφ = 0.35. (May/June 2009) (Apr/May 2008)
6. The standard heat of formation and standard free energy of formation of NH3 at 328 K are
-46,100 J/mol & 13,650 J/mol respectively. Calculate the equilibrium constant for the reaction.
N 2 ( g )  3H 2 ( g )  2 NH3 ( g ) at 500 K assuming that the standard heat of reaction is constant in
the temperature range of 328 K to 500 K. (Apr/May 2017)
PART – C
1. Explain how the equilibrium constants expressed for gas and liquid phase reactions.
(Apr/May2017) (Narayanan K.V“A Text Book of Chemical Engineering Thermodynamics”
Page No.404-407)
2. The gases from the pyrites burner of a contact sulphuric acid plant have the following composition:
SO2 = 7.8%, O2 = 10.8% and N2 = 81.4%. This is then passed into a converter where the SO2 is
converted to SO3. The temperature and pressure in the converter are 775 K and 1 bar. The
equilibrium constant for the reaction SO2+1/2 O2 → SO3 may be taken as
36
Ke =85. Calculate the composition of gases leaving the converter. (May/Jun 2016) (Narayanan
3. What is the influence of temperature on equilibrium constant and derive Van’t Hoff’s
equation.(Nov/Dec 2013) (Narayanan K.V“A Text Book of Chemical Engineering
4. (i) Describe the effect of reaction conditions on chemical equilibrium conversion.(Apr/May 2014)
(Narayanan K.V“A Text Book of Chemical Engineering Thermodynamics” Page No.422-
423)
(ii) Derive the equation relating equilibrium constant and standard free energy change.
(Apr/May 2014, 2010) (Narayanan K.V“A Text Book of Chemical Engineering
37
UNIT V -THERMODYNAMIC DESCRIPTION OF MICROBIAL GROWTH AND
PRODUCT FORMATION
PART A
1. Mention the expression for Gibbs energy for thermodynamics of maintenance. (Apr/May 2017)
The expression for Gibbs energy for thermodynamics of maintenance is given by
μ S

 - q max CS 
  mS YSXmax  
 K S  CS 
• CS = 0 ,  = mSYSXmax = -kd
• CS >>>,  = [-qSmax-(mS)]YSXmax = max
•  = 0, (-qS) = (-mS), which occurs at CS = CSmin.
2. Define specific growth rate. (Apr/May 2017)

It is defined as the rate of increase of biomass of a cell population per unit of biomass
concentration. It can be calculated in batch cultures, since during a defined period of time, the
rate of increase in biomass per unit of biomass concentration is constant and measurable.
3. What do you understand by Basal Metabolic rate? (May/June 2016)

Basal metabolic rate is the rate at which food is converted into heat transfer and work done
while the body is at complete rest. The body adjusts its basal metabolic rate to compensate
(partially) for over-eating or under-eating. The body will decrease the metabolic rate rather than
eliminate its own fat to replace lost food intake.
4. Brief on Herbert-Pirt equation. (May/June 2016)
μ
(qS )  max  (mS )
YSX
It means the substrates taken into cells are used for growth and maintenance only. Both mS and
YSXmax are model parameters.
Herbert-Pirt relation for substrate

μ
(  qS )  max
 (  mS )
YSX
It means the substrate taken into cells are used for growth and
maintenance only. Both mS and YSXmax are model parameters.
-qS 1
max
YSX
Herbert-Pirt linear plot for

substrate, non-catabolic
product is absent
(-mS)
0  5
Combination of the qS equation with Herbert-Pirt relation
μ S

 - q max CS 
  mS  Y 38 max
 K S  CS
SX

• CS = 0 ,  = mSYSXmax = -kd
• CS >>>,  = [-qSmax-(mS)]YSXmax = max
•  = 0, (-qS) = (-mS), which occurs at CS = CSmin.
The specific growth rate equation based on single substrate is then:
C  CSmin
μ  μ max S
K S  CS
5. Name the important parameters which describe growth of organism.
Growth of organisms is usually described by four parameters which belong to the hyperbolic
substrate uptake relation (μmax, ks) and the Herbert-Pirt relation (Ymaxsx, ms). The values of these
four parameters are essential to design processes in which growing organisms are used.
6. Define heterotrophic growth.

The biomass composition formula C1H1.8O0.5N0.2 shows that synthesis of biomass requires a
carbon source and an N-Source. In addition there is a need for an electron donor (D). When
growth uses an organic compound as substrate, then the substrate is both carbon and electron
donor. This is called heterotrophic growth.
7. Define autotrophic growth.

When growth uses CO2 as C-Source, then there is a need for a separate electron donor to reduce
CO2 to biomass. This is called autotrophic growth.
8. Define operational yield.

The operational yield YDX (Cmol X/mol electron donor) is defined as the ratio of μ and (-qD):
 max   
YDX   YDX  max 
 qD    (mDYDX 
9. Write the significance of operational biomass yield.

The operational biomass yield YDX is a hyperbolic function in μ.
At high μ : (μ >> (-mD YmaxDX)) the operational biomass yield approaches asymptotically the
maximum yield.
At low μ : (μ >> (-mD YmaxDX)) the operational biomass yield YDX drops to zero.
 max   
YDX   YDX  max 
 qD    (mDYDX 
10. Define Gibbs energy based coupling of catabolism to anabolism.
In catabolism, an electron acceptor performs a redox reaction with an electron donor leading to
the production of energy. This energy is coupled to anabolism to derive the anabolic reaction.
39
11. How Gibbs energy of a catabolic reaction is obtained?
The Gibbs energy of a catabolic reaction is obtained by first calculating the correct
stoichiometry of the complete catabolic reaction for the consumption of 1 mol electron donor,
after which are calculates  GR01  Gcat01
(which is the produced catabolic energy under
biochemical standard conditions.
12. Define biochemical standard conditions.

Biochemical standard conditions, indicated with superscript 01, (ie) 298 K, 1 bar, 1 mol/l, and
pH 7 (H+ concentration of 10-7 mol/l).
13. Write the equation for Heterotrophic growth.

a electron donor / C –source + b N- source + cH+ + dH20 +e CO2 + 1 C1H1.8 O0.5 N0.2 = 0
14. Write the equation for Autotrophic growth.

f CO2 +a electron donor / C –source + b N- source + cH+ + dH20 +e Oxidized electron donor + 1
C1H1.8 O0.5 N0.2 = 0.
15. Define degree of reduction.

Degree of reduction (δi) is a stoichiometric quantity which can be calculated for each chemical
compound for which the elemental composition is known. δ i reflects the amount of electrons
available in a compound.
16. How degree of reduction is calculated?

Degree of reduction δi is calculated by writing the redox half reaction in which compound i is
converted in a set of reference compounds which are CO2, H20, H+, Fe3+, N2 and electrons. The
amount of produced electrons equals δi..Using this redox half reaction approach we can calculate
the degree of reduction of elements and of electric charge.
17. How the complete stoichiometry of the anabolic reaction is obtained?

The complete stoichiometry of the anabolic reaction can be obtained from the elemental and
charge balances and that it can be calculated from the balance of degree of reduction that the
amount of electron donor needed in the anabolic reaction equals (δ X / δD) mol electron donor / C
mol X.
40
18. Write down the equations used to calculate the Gibbs energy of formation under nonstandard
condition?
The effect of nonstandard concentration at 25°C on Gibbs energy of formation (KJ/mol) of a
compound I follow from:
Dissolved compound: G fi  G 0fi  RT ln( Ci / 1)
Gaseous compound : G fi  G0fi  RT ln( Pi / 1)
Proton : G fi  39.87  RT ln( H  / 107 )
G f i is the Gibbs energy of formation.
C1/1 is the dissolved concentration of compound i (Ci, mol/l) divided by the standard con. (1
mol/l)
Pi/1 is the partial pressure of compound I (Pi atm), divided by the standard pressure (1 atm).
For H+ the biochemical standard is at H+ = 10-7 M
19. How the effect of temperature on the Gibbs energy of formation is obtained?
The effect of temperature (at standard concentration, pressure) on the Gibbs energy of formation
is obtained from the Van’t Hoff relation
G 0f (T )  H i  TS 0f
The value of the enthalpy of formation H 0f is obtained from the standard thermodynamic
tables.
20. Define ETC.

ETC – Electron Transport Chain. The ETC consists of electron processing proteins embedded in
membranes. Because cells are limited in the amount of membrane area and the amount of ETC
protein which can be placed in membranes is also physically (space) limited it is to be expected
that there is a limit in the electron transport rate per C mol X.
21. Define pmf.

Proton motive force (pmf). The pmf equals about 15 KJ of Gibbs energy for 1 mol H+, and
therefore one might expect that a catabolic reaction needs to generate at least 15 KJ of Gibbs
energy in order to create pmf.
22. Define yield factor.

Yield factor is used to quantify the nutrient requirements and production characteristics of an
organism.
23. Define Theoretical yield.

Theoretical yield is defined as the ratio of total mass or moles of product formed to mass or
moles of reactant used to form that particular product.
24. Define apparent yield.

Apparent yield is defined as the ratio of mass or moles of product present to total mass or moles
of reactant consumed.
41
25. Define observed yield.
Observed yield is particularly important for cell metabolism because there are always many
reactions occurring at the same time. The observed biomass yield based on total substrate
consumption is:
 X
'
YXS 
ST
26. Define RQ.
RQ –Respiratory Quotient.
RQ = e / a
RQ is defined as the moles of CO2 produced per mole of oxygen consumed. RQ values provide
an indication of metabolic state and can be used in process control.
27. Define overall and instantaneous yields.

∆F and ∆G can be calculated as the difference between initial and final values, this gives an
overall yield. If rF and rG are volumetric rates of production and consumption of F and G.
instantaneous yield may be calculated as follows:
 F  dF  dF / dt rF
YFG  lim   
G 0 G dG dG / dt rG
28. Define Ykcal.
Ykcal is defined as the ratio of mass or moles of biomass formed per kilocalorie of heat evolved
during fermentation.
29. Define yield.

Yield is defined as the ratio of amount of product formed or accumulated per amount of reactant
provided or consumed.
30. Define yield coefficient.

Yield coefficients can be written as,
 F
YFG 
G
YFG –yield factor. F and G are substances involved in metabolism
∆F – mass or moles of F produced
∆G- mass or moles of G consumed.
-ve sign is required because ∆G for a consumed substance is negative in value, yield is
calculated as a positive quantity.
31. Define Catabolism.
Catabolism is the pathway that breaks down molecules into smaller units and produces energy.
32. Define Anabolism

Anabolism is the building up of molecules from smaller units. Anabolism uses up the energy
produced by the catabolic break down of your food to create molecules more useful to your
body.
33. Give some examples of anabolic products.
(i) Amino acid
(ii) Nucleotide
(iii) Protein
42
(iv) Antibiotic
(v) lipid
34. Define doubling time.
Doubling time (td) is the time required for the concentration of biomass of a population of suspension
cells to double. One of the greatest contrasts between the growths of cultured plant cells refers to their
respective growth rates. The doubling time (td) can be calculated according to the following equation
35. Critical dilution rate

The maximal value for D (=µ) attainable in the chemostat, is achieved when the maximal CS in achieved.
At critical dilution rate, CS CS,in.
C S ,in  C S ,min
Dcrit  μ max  μ max
K S  C S ,in
PART B
1. Derive Herbert –Pirt Relation for electron donor consumption and explain the terms. (Apr/May
2017) (or) How to calculate the heat in operational stoichiometry using the Herbert –Pirt
Relation for Electron Donor. (Christiana D. Smolke, Page no. 11.4 – 11.17)
2. Explain the thermodynamic relation to calculate the biomass yield on electron donar. (Apr/May
2017) (or) Discuss about the thermodynamics of microbial growth stoichiometry. (May/Jun
2016) (Christiana D. Smolke, Page no. 11.2-11.3)
3. Explain about the formation thermodynamics. (May/Jun 2016) (Explain thermodynamics and
stoichiometry of Product Formation. (Christiana D. Smolke, Page no. 11.17-11.19)
4. Giving example find the stoichiometric coefficient for calculation of the anabolic reaction for
autotrophic growth. (Christiana D. Smolke, Page no. 11.3-11.4)
5. Giving example find the stoichiometric coefficient for calculation of the anabolic reaction for
heterotrophic growth. (Christiana D. Smolke, Page no. 11.3)
6. Calculate the stoichiometric coefficient and Gibbs free energy for catabolic reactions.
CH 4O  aNO3  bH   cN 2  dHCO3  eH 2O  0
Data:
Composition G 0f (KJ/mol)
H 2O -237.18
HCO3 -586.85
CO2 -394.359
 -39.87
H
CH4O -175.39
N2 0
NO3 -111.34
(Christiana D. Smolke, Page no. 11.7-11.9)

43
PART C
1. Explain in detail about calculation of the electron donor needed for anabolism using the balance of
degree of reduction. (Christiana D. Smolke, Page no. 11.4-11.5)
2. Write short notes on the elemental balance used in stoichiometric calculations. (Apr/May 2015)(Class
notes)
3. Write in detail about the correlations to find the amount of Gibbs energy generated in the anabolic
reaction for the synthesis of 1 Cmol of synthesis.
(Christiana D. Smolke, Page no. 11.10-11.12)
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JEPPIAAR ENGINEERING COLLEGE

B.TECH – BIOTECHNOLOGY (R- 2017)

BT 8302 APPLIED THERMODYNAMICS FOR

II YEAR & III SEM

PROGRAM OUTCOMES (PO)

To pursue excellence in producing bioengineers coupled with research attributes.

MISSION OF THE DEPARTMENT

M3 To generate societal conscious technocrats towards community development

PROGRAM EDUCATIONAL OBJECTIVES (PEOS)

PEO - 3 To connect the program and community by fostering technical education.

PEO - 4 To provide a wide technical exposure to work in an interdisciplinary environment

PROGRAM SPECIFIC OUTCOMES (PSOS)

BT 8302 APPLIED THERMODYNAMICS FOR BIOTECHNOLOGISTS

2. What is ‘equation of state’? (Apr/May 2017)

3. Discuss on volume expansivity. (May/June 2016)

4. Define the principle of corresponding states. (May/June 2016)

3 Internal energy is a Kinetic Energy is not a Potential Energy is not a

State Function Path Function

Depends only on the state at the Dependent on path taken to

8. Define CP and Cv. (May/June 2014)

At constant volume (isometric), CV = molar specific heat at constant V

10. Define Helmholtz energy. (May/June 2013,2012)

11. What are residual properties? (May/June 2012) (Apr/May 2010)

Fundamental property relations

14. Define-volume expansivity and isothermal compressibility. (Apr/May 2011)

16. Define system.(Nov/Dec 2009)

17. Define system and surroundings. (Nov/Dec 2009)

18. What is physical significance of virial coefficients? (Apr/May 2008)

19. What is compressibility factor? (Apr/May 2008)

21. What is control volume? (Nov/Dec 2008)

23. State first law of thermodynamics. (May/June 2006)

25. Define a closed system with one example. (Nov/Dec 2003)

26. Define an open system with one example.(Nov/Dec 2003)

27. Define Clausius inequality.

29. Define the term: Extensive property.

30. State the commonly used equation for equations of state.

31. Define equilibrium state.

32. Define triple point of water.

33. State Avogadro’s hypothesis.

3. Differentiate between Clapeyron and Clausius-Clapeyron equations. (May/June 2016) (Apr/May

4. What is meant by partial molar property?(May/June 2016) (Apr/May 2011,2008)(Nov/Dec 2010,2009)

8. State Gibbs Duhem equation.(Nov/Dec 2013) (May/June 2006)

11. What are the characteristics of an ideal solution? (Apr/May 2011,2008)

13. Define fugacity coefficient. (Apr/May 2010)

18. What is a heat pump? (Nov/Dec 2009)

19. Define fugacity for a real gas. (Apr/May 2008)(Nov/Dec 2008)

22. Define COP of refrigerator. (Nov/Dec 2008)

26. State Lewis fugacity rule. (Nov/Dec 2013)

29. State lewis Randall rule.

30. Define partial molar volume.

33. State the Characteristics of Entropy.

34. State conditions of Lewis fugacity rule.

1. Derive an expression for fugacity and fugacity coefficient of pure species.(APR/MAY

1 The first bubble of vapour is The first drop of condensate is formed on

3 At bubble point, ∑yi = ∑ki xi = 1 At dew point, ∑ xi = ∑ yi / ki = 1

7. What is Poynting correction? (May/June 2014)

12. What is the criterion for liquid-liquid equilibrium? (Apr/May 2010)

16. State Gibb’s phase rule. (Nov/Dec 2010)

17. List the criteria for phase equilibrium. (Nov/Dec 2010)

20. How many types of azeotropes are there? (May/June 2009)

21. Define equilibrium in terms of chemical potential. (Nov/Dec 2009)

22. Define isochoric process. (Nov/Dec 2009)

23. Why does immiscibility occur in liquid solutions? (May/June 2009)